Catalysts comprising layered chalcogenides of group IVb-group VIIb prepared by a low temperature nonaqueous precipitate technique

ABSTRACT

In processes for the catalytic treatment of hydrocarbon feedstream containing organic sulfur comprising contacting said feedstream with a catalyst for a time at a temperature and pressure sufficient to effect the desired catalytic change on the feedstream, the improvement comprising using as the catalyst a layered composition of the formula MX y  wherein M is a transition metal selected from the group consisting of Group IVb, Vb, VIb, VIIb and uranium, X is a chalcogen selected from the group consisting of sulfur, selenium, tellurium, and mixtures thereof, y is a number ranging from about 1.5 to about 3. The catalyst is prepared by reacting neat or in the presence of a nonaqueous solvent a Group IVb to VIIb or uranium metal salt, and a source of sulfide, selenide or telluride ions, and mixing the reactants at temperatures below 400° C. and at atmospheric pressures. The catalyst may be isolated by filtration and washing with excess solvent (when one is used) or by vacuum pumping any volatile coproduced anion salt. Preferably the chalcogenide is sulfur and y is about 1.5 to about 2. 
     The catalytic processes which are benefited by the use therein of the above-described compositions are hydrodesulfurization, hydrodenitrogenation, hydroconversion and hydrogenation run in the presence of hydrogen or a hydrogen donor solvent.

This is a continuation, of application Ser. No. 973,715, filed Dec. 26,1978 which is a Rule 60 Continuation of Ser. No. 797,012 filed May 16,1977, both abandoned.

BRIEF DESCRIPTION OF THE INVENTION

An improved process is described for the catalytic treatment ofhydrocarbon feedstream containing organic sulfur such as coalliquefaction products and heavy resid oils which comprises contactingsaid feedstream hydrogen with a catalyst at a temperature and hydrogenpressure and for a time sufficient to effect the desired change in thefeed, the improvement comprising using as the catalyst a layeredcomposition of the formula MX_(y) wherein M is a transition metalselected from the group consisting of Group IVb, Vb, VIb, VIIb anduranium, X is a chalcogen selected from the group consisting of sulfur,selenium, tellurium and mixtures thereof, preferably sulfur andselenium, most preferably sulfur, Y is a number ranging from about 1.5to about 3. The catalytic materials have a crystalline size of about 50A×100 A or less and a particle size of 0.1 micron or less, preferably0.05 micron or less. The catalyst is prepared by reacting neat or in thepresence of an added nonaqueous solvent, the desired Group IVb to VIIbmetal salt or salts, the anion, of the salt preferably selected from thegroup consisting of halide (preferably chloride), acetate, carboxylate,nitrate and sulfate and a source of sulfide, selenide or telluride ions,said source being selected from the group consisting of Li₂ X, Na₂ X, K₂X, NaHX, LiHX, NH₄ HX, KHX, (NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂X wherein R, R' and R" are the same or different C₁ -C₂₀ alkyl, C₆ -C₂₀aryl, preferably C₁ -C₈ alkyl, C₆ -C₁₂ aryl and X is a chalcogenselected from the group consisting of sulfur, selenium, tellurium andmixtures thereof, preferably sulfur and selenium, most preferablysulfur. The nonaqueous solvent (if one is used) is selected from thegroup consisting of ethers having 4-8 carbons, acetonitrile,benzonitrile, pyridine, propionitrile, N-methylformamide,dimethylformamide (DMF), 1,2-dimethoxyethane (DME), propylene carbonate,ammonia, C₆ -C₂₀ aromatics, molten sulfur, sulfur dioxide, diglyme,ethylacetate, esters of from C₄ to C₁, sulfolane, dimethylsulfite,tributylphosphate, C₁ -C₃₀ amines, C₅ -C₁₂ alkanes, anhydrous acids,alkylhalides of from 1-20 carbons and aryl halides of from 6-20 carbonswherein the halide is selected from the group consisting of Cl, Br andI, and the hydrocarbon feed to be catalytically treated. The catalyst isprepared spontaneously upon mixing the reactant at temperatures below400° C. and at atmospheric pressures. The catalyst may be isolated byfiltration and washing with excess solvent (when one is used) or byvacuum pumping any volatile coproduced anion salt. Preferably thechalcogen is sulfur and y is 2.

The catalytic material can be prepared outside the catalytic reactor orit can be prepared in the reactor itself by the introduction of theappropriate, desired starting materials (as outlined above) into thereactor using the hydrocarbon feed as the nonaqueous solvent.

The catalytic processes which are benefited by the use therein of theabove-described compositions are hydrodesulfurization,hydrodenitrogenation, hydroconversion and hydrogenation.

Typically, the catalytic processes are run at temperatures ranging fromambient to 500° C., preferably 100°-450° C., most preferably 200°-400°C. at pressures of from 1 atm to 5000 psig H₂, preferably 100 to 2000psig H₂ and at space velocities of 0.1→10 V/V/Hr, preferably 0.1→5V/V/hr.

Petroleum crude oils and especially the heavy residuals and shale oiland tar sand oils derived therefrom contain sulfurous compound in largequantities. The liquefaction products obtained from coal also containconsiderable quantities of organic sulfur compound. Typically sulfurcontent for the various hydrocarbon feedstreams is in the range of fromabout 1 to about 6 percent. Because of the deleterious effects sulfurcompounds have on the environment it is necessary to remove most, if notall of the organic sulfur from the hydrocarbons before thesehydrocarbons are useable as fuels. Consequently, new and improvedprocesses and catalysts for effecting this removal are constantly beingsought.

In the past transition metals of from Group IVb to VII have been used toeffect this hydrodesulfurization. Such metals, however, quicklydeactivate. To overcome this, metal sulfides have been utilized as HDScatalysts.

The literature is repleat with descriptions of hydrogenation andhydrodesulfurization processes utilizing sulfided IVb to VIIb metals insupported and unsupported condition. See for instance, U.S. Pat. No.1,932,369; 3,694,350. U.S. Pat. No. 3,840,473 describe ahydrodesulfurization process using phosphate-free catalysts of Group VIand/or Group VIII metals, their oxides or sulfides on a nonzeolitecarrier, with addition of 1-10 wt. % Group IVb metal (Ti, Zr, or Ag) aspromoter.

U.S. Pat. No. 2,835,349 to Hansford describes a process forhydrocracking and desulfurizing a mineral oil feedstock containing atleast about 0.1% S which comprises contacting the feedstock with acatalyst in the absence of H₂ O and O₂ but with about 1000 to 10,000 SCFof H₂ /barrel of feed wherein the catalyst comprises a major portion ofan adsorbent acidic oxide carrier having cracking activities and a minorportion of chromium sulfide at temperatures, pressures and spacevelocities sufficient to effect the conversion. The chromium sulfide isprepared by the reduction of chromium sulfate which has been depositedin the carrier from aqueous solution.

U.S. Pat. No. 2,531,767 to Chenicek teaches the use of Mo sulfide as HDScatalyst.

G.B. Pat. No. 362,354 describes a desulfurization process using rheniumor compounds thereof brought in colloidal form onto suitable carrierstogether with other metals or compounds. In an example a catalytic massconsisting of molybdenum oxide in carbon and rhenium sulfide (ReS₂) incarbon was used to desulfurize a light Venezuelan motor cylinder oilcontaining 0.41% S. The end product obtained contained 0.16% S.

It has been discovered, and forms the basis of this disclosure, thatcatalytic process and hydrodesulfurization processes in particular,utilizing catalysts can be improved in terms of activity, andselectively by using as a catalyst a layered composition of the formulaMX_(y) wherein M is a transition metal selected from the groupconsisting of Groups IVb, Vb, VIb, VIIb, and uranium, X is a chalcogenselected from the group consisting of sulfur, selenium, tellurium andmixtures thereof, preferably sulfur and selenium, most preferablysulfur, and y is a number ranging from about 1.5 to about 3.0 whichcatalyst is prepared by reacting neat or in the presence of an addednonaqueous solvent a Group IVb to VIIb or uranium metal salt, the anionof the salt typically being selected from the group consisting of halide(preferably chloride, bromide and iodide), acetate, carboxylate,perfluorocarboxylate, acetylacetonate, hexafluoroacetonate, sulfate andnitrate and a source of sulfide, selenide or telluride ion, said sourcebeing selected from the group consisting of Li₂ X, Na₂ X, K₂ X, NaHX,LiHX, KHX, NH₄ HX, (NH₄)₂ X, (RNH₃)₂ X, (RR'NH.sub. 2)₂ X, (RR'R"NH)₂ Xwherein R, R' and R" are the same or different C₁ -C₂₀ alkyl, C₆ -C₂₀aryl, preferably C₁ -C₈ alkyl, C₆ -C₁₂ aryl and X is a chalcogenselected from the group consisting of sulfur, selenium, tellurium andmixtures thereof, preferably sulfur and selenium, most preferablysulfur. The nonaqueous solvent (if one is used) is selected from thegroup consisting of C₄ -C₈ ethers, acetonitrile, benzonitrile, pyridine,propionitrile, N-methylformamide, dimethylformamide (DMF),1,2-dimethoxyethane (DME), propylene carbonate, ammonia, C₆ -C₂₀aromatics, molten sulfur, sulfur dioxide, diglyme, ethylacetate, C₄ -C₁esters, sulfolane, dimethylsulfite, tributylphosphate, C₁ -C₃₀ amines,C₁ -C₁₂ alkanes, anhydrous acids, C₁ -C₂₀ alkyl halides and C₆ -C₂₀arylhalides wherein the halide is selected from the group consisting ofCl, Br and I and the hydrocarbon feedstream to be catalytically treated.Solvents of choice include tetrahydrofuran (THF), dimethylformamide(DMF), chlorobenzene, chloroform, pyridine, acetone and propylenecarbonate. The catalyst is prepared spontaneously upon mixing thereactants at temperatures below 400° C. (but greater than about -78°C.), the temperature selected being such that the reactants remain inthe liquid state, i.e. above the freezing point but below thevaporization point and at atmospheric pressure. The catalyst may beisolated by filtration and washing with excess solvent (when a solventis used) or by vacuum pumping any volatile coproduced anion salt.

The catalytic material can be prepared outside the catalytic reactor orit can be prepared in the reactor itself by the introduction of theappropriate, desired starting materials (as outlined above) into thereactor using the hydrocarbon feed as the nonaqueous solvent.

The catalytic processes which are benefited by the use therein of theabove-described compositions are hydrodesulfurization,hydrodenitrogenation, hydroconversion and hydrogenation.

Typically, a metal salt of the transition metal such as TiCl₄ is reactedwith a nonaqueous solution of, or a slurry of a convenient sulfide,selenide or telluride ion source such as Li₂ S, hydrosulfide salt (i.e.LiHS, NH₄ HS, KHS, NaHS), (NH₄)₂ S, Na₂ S, K₂ S (RNH₃)₂ S, (RR'NH₂)₂ S,(RR'R"NH)₂ S wherein R, R' and R" are the same or different C₁ -C₂₀alkyl or C₆ -C₂₀ aryl, preferably C₁ to C₈ alkyl or C₆ -C₁₂ aryl, Li₂Se, Li₂ Te, (NH₄)₂ Se in a nonaqueous solvent such as THF, ethers,acetonitrile, propylene carbonate, DMF, molten sulfur, etc. The reactionwhich takes place is: ##EQU1## M=all Group IVb, Vb, VIb or VIIbtransition metals or uranium; A=alkali metal, NH₄ ⁺, RR'R"NH⁺, or othercation as defined above; Z=convenient anion such as Cl, Br, I, acetate,carboxylate, nitrate, etc., as recited above, X=sulfur, selenium ortellurium.

Any convenient source of M⁺²⁻⁺⁵, preferably M⁺⁵, most preferably M⁺⁴ canbe used. Complexes formed in solution which can be isolated as solidsmay be used as M⁺⁴ source. In some cases (such as Nb and Ta) apentavalent salt may be used directly because reduction of M⁺⁵ to M⁺⁴occurs, for example:

    NbCl.sub.5 +2.5 Li.sub.2 S→NbS.sub.2 ↓+5LiCl+0.5 S

The reaction is normally but not necessarily conducted in the absence ofan excess of sulfide, selenide or telluride ion sources although otherstarting materials may be present in excess. Since particle size dependson the rate of mixing of reagents, the reaction may be allowed toproceed instantly, upon total admixture of one reagent to the reactionsolution yielding fine products, or upon the measured addition of smallincrements of one reagent to the reaction solution, the reaction notachieving totality for several days.

As previously stated, the reagents may be mixed neat, i.e., no addedsolvent, when this is feasible, or may be diluted with solvent. The useof solvent, therefore, is not critical to the reaction; however, when asolvent is utilized, it must be nonaqueous.

The temperature of the reaction may range from +78° to 400° C.,preferably ambient (25° C.) to 300° C. These temperatures are markedlylower than those needed when preparing dichalcogenides via solid stateor gas phase methods wherein reaction temperatures up to and exceeding1000° C. are commonplace.

The improved process utilizing the above enumerated catalyst prepared bythe recited procedure may be used on a supported or unsupported form.When supports are used the materials may be deposited on the support byabsorption of the metal sulfide from a homogeneous dispersion producedby reacting the reagents in certain solvents such as propylenecarbonate, in the presence of the support, which supports are anytypical inert or refractory oxide material, such as carbon, charcoal,alumina, silica, silica-alumina, MgO, CaO, the oxides of Groups IV-VI,especially TiO₂, ZrO₂, ZrTiO₄, etc. The most preferred supports,however, when one is used are MgO, CaO, alumina, silica-alumina and highsurface area carbon.

EXAMPLE 1 Preparation of TiS₂ (ZrS₂, HfS₂ and VS₂)

The following example employs as a starting material TiCl₄. It was foundthat the procedure worked equally well for ZrCl₄, HfCl₄, MoCl₄ or VCl₄.A solution of 10 millimoles of TiCl₄ (1.9 g) in tetrahydrofuran (75 ml)was made up in a dry box (TiCl₄ is not stable in air or moisture). Tothis stirred solution at room temperature was added 0.96 g (20millimoles) of lithium sulfide. The yellowish solution immediately beganto darken. The reaction was allowed to proceed several hours although itwas essentially complete within one hour. The resulting dark brown solidwas filtered and washed with 10 ml THF. From the combined filtrates 83%of calculated ideal yield of lithium chloride was isolated afterevaporation of the solvent. An elemental analysis of the dark brownpowder remaining after drying revealed it to be TiS₂ containing one-halfmole of solvent tetrahydrofuran and less than 5% by weight LiCl. Beforecatalytic evaluation the powders were heated at 400° C. in a stream ofH₂ /H₂ S for 1 hour, cooled, then washed with 12% acetic acid; thenreheated in a H₂ /H₂ S stream for one hour after which the chemicalanalysis showed only metal and sulfur with approximately 2:1 sulfur tometal ratio. The practice of the sulfiding step, however, is notessential to the successful practicing of the instant disclosedinvention, it merely being an optional preferred step.

EXAMPLE 2 Preparation of NbS₂ (TaS₂)

This procedure is applicable to those transition metals of Group Vb andVIIb which form pentahalides (Nb and Ta and Re) and the example is givenfor niobium pentachloride:

To a solution of 10 millimoles of NbCl₅ (2.68 g) in 50 mltetrahydrofuran was added 1.15 g lithium sulfide (25 millimoles) and thereaction stirred in the dry box overnight. The dark product obtained onfiltration was shown to contain 60% by weight NbS₁.97. This sample wasthen treated as in previous example upon which the sample was close to100% NbS₁.97.

EXAMPLE 3 Preparation of Molybdenum Disulfide

Addition of 10 millimoles of molybdenum tetrachloride and 20 millimolesof lithium sulfide to 30 ml THF with stirring results in a fine blacksolid which on filtration and drying contains 70% by weight/MoS₂. Mostof the additional weight (60%) can be attributed to solvent which can beremoved by heating to ca 150° C. and pumping (1 torr). As aboveexamples, a H₂ /H₂ S, 12% acetic H₂ /H₂ S treatment yielded a blackpowder.

EXAMPLE 4 Li₂ Se+ZrCl₄, ZrSe₂

Into 50 ml acetonitrile, 10 millimoles zirconium tetrachloride is addedand then, with stirring 20 millimoles of lithium selenide is addedportionwise. After allowing to stir several hours, the solid product iscollected on a filter and washed with acetonitrile and dried. Thus, 10millimoles of zirconium diselenide is afforded.

EXAMPLE 5 Neat Preparation of Crystalline TiS₂ from NH₃, H₂ S and TiCl₄

Into a three-necked flask, a quantity of (approximately 5 grams) of(NH₄)HS or (NH₄)₂ S was prepared by flowing in NH₃ gas and H₂ S gas. Tothe resulting white solid 3.8 gms of TiCl₄ (20 mmol) was added dropwise.A reaction immediately occurred yielding a black-brown solid, which wasTiS₂ +(NH₄)Cl. This black-brown solid was removed from the flask andsealed in vacuum in a 20 mm diameter quartz tube which was 25 in. long.The tube was placed in a temperature gradient with one end at 380° C.and the other at 100° C. for one day. (NH₄)Cl sublimed and condensed atthe colder end thus effecting separation. At the hot end, the TiS₂annealed yielding a perfect crystalline x-ray powder pattern.

EXAMPLE 6 ReS₂ From ReCl₅ by the Reaction ReCl₅ + 2.5 Li₂S→5LiCl+1/2S°+ReS₂

3.64 gms of KeCl₅ were reacted with 2.30 gms of Li₂ S in 100 mlethylacetate and allowed to stir. The black product as filtered anddried in H₂ S at 400° C. The product yielded an analysis for ReS₂.0.

    ______________________________________                                                    Theoretical                                                                           Measured                                                  ______________________________________                                        % Re          74.39     74.40                                                 % S           25.61     25.49                                                 ______________________________________                                    

The X-ray product corresponded to ReS₂ and line broadening indicated acrystallite size of about 40×80 A. A BET surface area yielded 50.2 m²/gm. Product before heat treatment was completely amorphous to X-raysindicating a crystalline order to less than 5 A, thus an amorphoussolid.

EXAMPLE 7 ReS₂ From ReCl₄ by the Reaction ReCl₄ + 2Li₂ S→ReS₂ +4 LiCl

In an exactly analogous manner to Example 6, ReS₂ was prepared fromReCl₄ with the same results except that excess sulfur did not have to beremoved by washing or heating.

EXAMPLE 8 ReS₂ Dispersions

2.83 grams (8 mm) of ReCl₅ was added to 80 ml of propylene carbonate. Tothis was added 0.89 gms of Li₂ S (19 mm) and the solution was stirredfor 4 hours yielding a black liquid which was 0.1 M in ReS₂ and could becontinuously diluted to any concentration. This black liquid passedthrough normal filter discs and was stable.

EXAMPLE 9 ReS₂ /MgO Composite

An 0.1 M dispersion of ReS₂ in propylene carbonate was prepared as inExample 8. 25 ml of this dispersion was contacted with 4 gms of MgO andstirred for 4 hours. The initially white solid was filtered and dried inH₂ S at 400° C. for 1 hour yielding a dark gray solid. The solid ReS₂/MgO composite was analyzed for ReS₂ yielding 2.33% Re. The amount ofReS₂ absorbed on the MgO can be controlled by varying the stir time andconcentration.

EXAMPLE 10 Stable Homogeneous Dispersions

If the reactions MoCl₄ +A₂ S herein described wherein A is as previouslydefined, are carried out in appropriate media, stable homogeneousdispersions of MoS₂ in the liquid result (either accompanied or in theabsence of the precipitated solid). Appropriate solvents includepropylene carbonate, dimethylformamide (DMF), pyridine, acetonitrile,benzonitrile, propionitrile, 1,2 dimethoxyethane, diglyme,N-methylformamide. Use of these solvents results in the formation ofhomogeneous dispersions in the cases of all the Group IV through VII anduranium chalcogenides so far disclosed. For instance, if propylenecarbonate (PC) is used as solvent, the supernatant phase will be a darkbrown opaque dispersion which is unchanged on filtration (medium fritfunnel) and which does not settle out over a period of weeks or months.Alternatively, if in addition to a nondispersing solvent (such as THF) adispersing agent such as pyridine (or alkylamines) is initially presenta similar dispersion will result. Murphy and Hull (J. Chem. Phys. 62 973(1975)) have described dispersions of TaS₂ in aqueous media which areconsiderably less stable due to eventual decomposition of the sulfide bywater (hydrolysis). In nonaqueous solutions such as those described inthe instant invention such decomposition does not occur and stabilityremains for months.

The reaction of a solution of TiCl₄ in excessive trihexylamine andtetrahydrofuran with hydrogen sulfide provides another example of ameans of dispersing the product TiS₂ in the media. The presense of theamine in the reaction media serves to disperse the extremely fineparticles of the product they form. The chalcogenides formed in suchdispersions may be absorbed on high surface area carbons, refractoryoxides and high surface area basic or acidic solids such as CaO, MgO,Al₂ O₃, silica-alumina, the solution clearing with time. Any othercatalyst may be dispersed by substituting the appropriate metal halide(MoCl₄, ReCl₄, etc.).

As Hydrodesulfurization Catalysts

A. Materials of the formula MX_(y) wherein M, X and y are as previouslydefined and which materials are prepared in accordance with theprocedures outlined herein are superior hydrodesulfurization catalysts.The desulfurization of dibenzothiophene is an industry wide, acceptedtest of the HDS activity of various material. These materialsdesulfurize dibenzothiophene (DBT) at temperatures ≧300° C. and hydrogenpressure ≧250 psi according to reaction (1) yielding biphenyl (BP) andcyclohexylbenzene (CHB): ##STR1## The amount of cyclohexylbenzene formedis used as a measure of the hydrogenation activity of the sulfide in asulfur or H₂ S environment, for 2.0 hrs. at 25° C.-400° C.

The catalyst pretreatment entails exposure to 15% H₂ S/H₂ (55 cc/min)for 2 hours at 25°-400° C. When appropriate the novel materials arecompared to prior art binary sulfides and to commercial cobalt molybdateon γ-alumina, the hydrodesulfurization work-horse of the industry.

The rate constants for the desulfurization of dibenzothiophene for theunsupported materials were calculated (a) per gram of material; (b) permillimole of metal and are reported in Table I.

                                      TABLE I                                     __________________________________________________________________________    HYDRODESULFURIZATION ACTIVITY OF GROUP IVB-VIIB BINARY SULFIDES               Conditions: Carberry Reactor, 400° C., 450 psi, 10/20 mesh             catalyst particles                                                                   Activity           Activity                                             Catalyst                                                                             ##STR2##                                                                                         ##STR3##                                           __________________________________________________________________________    Group IVB                                                                     TiS.sub.2                                                                            1.2                1.4                                                 ZrS.sub.2                                                                            0.8                1.2                                                 Group VB                                                                      VS.sub.2-x                                                                           1.0                1.1                                                 NbS.sub.2                                                                            1.1                1.7                                                 TaS.sub.2                                                                            0.4                1.1                                                 Group VIB                                                                     Cr.sub.2 S.sub.3                                                                     4.8                4.8                                                 MoS.sub.2                                                                            5.0                8.0                                                 WS.sub.2                                                                             1.3                3.2                                                 Group VIIB                                                                    MnS    0.7                0.6                                                 ReS.sub.2                                                                            16.0               39.4                                                __________________________________________________________________________

The rate constant per gram of catalyst for commercial cobalt-molybdate(Nalco-JCM 468) on γ-alumina under identical conditions is 67×10¹⁶molecules of dibenzothiophene converted/gm-sec.

The literature teaches that layered sulfides prepared according to priorart reactions (2) and (3): ##STR4## are catalytically active fordesulfurization reactions. However, the materials prepared by reactionsdescribed in the preceding part of the patent application are moreactive per unit gram of material under the same conditions oftemperature, pressure, catalyst mesh and quantity. The comparative datais summarized in Table II. Materials 2 and 5 are prepared via thenonaqueous precipitation technique described herein while materials 1, 3and 4 are prepared by typical prior art techniques: clearly, thenonaqueous precipitation technique yields superior catalysts.

                                      TABLE II                                    __________________________________________________________________________    EFFECT OF PREPARATION ON HYDRODESULFURIZATION ACTIVITY                        Conditions: Carberry Reactor, 400° C., 450 psi, 10/20 mesh                                Activity                                                    Material                                                                           Method of Preparation                                                                       ##STR5##                                                  __________________________________________________________________________    (1) NbS.sub.2                                                                      Nb + S; Rxn 2 11                                                         (2) NbS.sub.2                                                                      Nonaqueous precipitation                                                                    17                                                         (3) MoS.sub.2                                                                      NH.sub.4 MoS.sub.4 ; Rxn 3                                                                  22                                                         (4) MoS.sub.2                                                                       ##STR6##                                                                        25-400° C. 90 min                                                   (4928-42) 400° 30 min                                             (5) MoS.sub.2                                                                      Nonaqueous precipitation                                                                    50                                                         __________________________________________________________________________     + 10/40 mesh, conversion to MoS.sub.2 not completed.                     

B. ReS_(y) (wherein y is about 1.5 to about 4) materials prepared by thenonaqueous precipitation technique described in detail above aresuperior HDS type catalysts compared to RES_(y) materials prepared byprior art technique. This can be seen from Tables III and IV whereinReS_(y) type materials are compared for their activity/gram for theconversion of dibenzothiophene (DBT). In Table III, materials 1 and 2are prepared by the nonaqueous precipitation technique described hereinwhile material 3 is prepared by a typical prior art technique. Clearly,the nonaqueous precipitation materials are superior.

                                      TABLE III                                   __________________________________________________________________________    EFFECT OF PREPARATION ON HYDRODESULFURIZATION ACTIVITY                        Conditions: Carberry Reactor, 400° C., 450 psi, 20/40 mesh                                   Activity                                                 Catalyst                                                                               Method of Preparation                                                                      ##STR7##                                               __________________________________________________________________________    (1) ReS.sub.2ReS.sub.2-x                                                               Nonaqueous Precipitation                                                                   50.3                                                             from ReCl.sub.5 + Li.sub.2 S                                         (2) ReS.sub.2ReS.sub.2-x                                                               Nonaqueous Precipitation                                                                   164                                                              from ReCl.sub.4 + Li.sub.2 S                                          (3) ReS.sub.2                                                                          ##STR8##    4.7                                                              From the elements                                                    __________________________________________________________________________

In Table IV, the ReS_(y) type materials are compared for theiractivity/gm for the desulfurization of dibenzothiophene (DBT) tobiphenyl (BP) and their hydrogenation activity as reflected incyclohexylbenzene reaction rates. Materials 1, 2 and 3 are prepared bythe nonaqueous precipitation while material 4 is prepared by a typicalprior art technique. The nonaqueous precipitation materials are againclearly superior HDS and hydrogenation catalysts; indeed their activityper gram is superior to a commercial cobalt molybdate on γ-aluminacatalyst (CMA) material.

                                      TABLE IV                                    __________________________________________________________________________    COMPARISON OF CATALYSTS FOR HYDRODESULFURIZATION AND                          HYDROGENATION ACTIVITY                                                        Conditions: Carberry Reactor, 350° C., 450 psi, 20/40 mesh                                     Activity                                                                       ##STR9##                                              Catalyst Method of Preparation                                                                       x = BP                                                                             CHB    Total                                     __________________________________________________________________________    (1) ReS.sub.2ReS.sub.2-x                                                               Nonaqueous precipitation                                                                    13.0     Non-detected                                                                         13.0                                            from ReCl.sub.5 + Li.sub.2 S                                         (2) ReS.sub.2ReS.sub.2-x                                                               Nonaqueous precipitation                                                                    63       8      71                                              from ReCl.sub.4 + Li.sub.2 S                                         (3) ReS.sub.2ReS.sub.2-x                                                               Nonaqueous precipitation                                                                    2        Non-detected                                                                         2                                               from ReCl.sub.3 + Li.sub.2 S                                         (4) Re.sub.2 S.sub.7                                                                   Prior art preparation                                                                       3        Non-detected                                                                         3                                               technique                                                                      ##STR10##                                                           (5) CMA  Commercial    51       6      57                                     __________________________________________________________________________

C. RoS₂ supported on refractory oxides and high surface area basic oracidic solids such as MgO, CaO, γ-Al₂ O₃ according to the followingprocedure, reaction (5) are active hydrodesulfurization catalysts forresid-like organosulfur molecules (i.e. dibenzothiophene): ##STR11##

In Table V, the hydrodesulfurization activity of ReS₂ supportedcatalysts prepared by the nonaqueous dispersion technique on variousacidic and basic supports described herein are compared with supportedrhenium catalysts prepared by typical prior art techniques. Thecatalysts are compared in two ways: (a) activity/gram and (b)activity/millimole of metal.

In general, when utilizing a Group IVb to Group VIIb or uraniumchalcogenide in the supported state the metal chalcogenide will bepresent at from 0.01 to 30 wt % Group IVb to Group VIIb or uranium metalbased on total catalyst, preferably from 0.1 to 10 wt. % Group IVb toGroup VIIb or uranium metal based on total catalyst.

                                      TABLE V                                     __________________________________________________________________________    EFFECT OF PREPARATION ON THE HYDRODESULFURIZATION ACTIVITY OF SUPPORTED       RHENIUM SULFIDE CATALYSTS                                                     Conditions: Carberry Reactor, 350° C., 450 psi, 20/40 mesh                                    Activity        Activity                                                      r ×10.sup.16 molecules of DBT →                                                  r × 10.sup.16 molecules DBT                                             → X                                                    gm-sec          gm millimoles Re                       Catalyst Method of Preparation                                                                       x = BP                                                                              CHB  Total                                                                              BP   CHB Total                         __________________________________________________________________________    (1)                                                                             ReS.sub.2 /MgO                                                                       Nonaqueous dispersion                                                                       9.4   --   9.4  88   --  88                              (2% Re)                                                                              from ReCl.sub.5 + Li.sub.2 S                                         (2)                                                                             ReS.sub.2 /MgO                                                                       Nonaqueous dispersion                                                                       2.8   --   2.8  86   --  86                              (0.6% Re)                                                                            from ReCl.sub.4 + Li.sub.2 S                                         (3)                                                                             ReS.sub.2 /γAl.sub.2 O.sub.3                                                   Nonaqueous dispersion                                                                       7.4   --   7.4  84   --  84                              (1.64% Re)                                                                           from ReCl.sub.5 + Li.sub.2 S                                         (4)                                                                             ReS.sub.2 /γAl.sub.2 O.sub.3                                                   NH.sub.4 ReO.sub.4 (aqueous impreg-                                                         11    0.6  11.6 110  6   116                             (1.91% Re)                                                                           nation) Dry Vacuum 700° C.)                                            Presulfide 15% H.sub.2 S/H.sub.2,                                             25-400° C., 2 hrs.                                            (5)                                                                             ReS.sub.2 /γAl.sub.2 O.sub.3                                                   NH.sub.4 ReO.sub.4 (Aqueous impreg-                                                         8.4   --   8.4  84   --  84                              (1.91% Re)                                                                           nation) Dry, Calcine                                                          3 hrs, 450° C. air, Presulfide                                (6)                                                                             ReS.sub.2 /MgO                                                                       Same as 4     4.2   --   4.2  37.7 --  37.7                            (2.05% Re)                                                                  (7)                                                                             ReS.sub.2 /MgO                                                                       Same as 5     2.1   --   2.1  21   --  21                              (2.05% Re)                                                                  __________________________________________________________________________

An activity comparison of the γ-Al₂ O₃ supported rhenium catalystsindicates that the nonaqueous dispersion material, compound 3, displayscomparable activity to prior art material 5. Material 4 however,displays the best activity of the alumina supported catalysts. Theactivity of this material was increased considerably by the eliminationof the calcination step. Consequently prior art techniques in whichcalcination at elevated temperatures in air are routine yield inferiorcatalytic materials for hydrodesulfurization.

The activity advantage of the nonaqueous dispersion preparation overaqueous methods is more dramatic when the desired support is MgO. Inthis case, the activity is two to four times higher than prior artmaterials; material 1 is 2.2-4.5 times more active per gram and permillimole of rhenium than materials 6 and 7 respectively.

In Table VI, the hydrosulfurization activity of ReS₂ (2.1% Re)/MgO ispresented and compared to cobalt-moly/γ-Al₂ O₃, CMA (JCM-468, RT-2) at400° C. and 450 psig, H₂ flow˜100 cc/min.

Table VI indicates that under comparable conditions but with lower metalloading and less catalyst, ReS₂ (2.1% Re)/MgO is approximately as activeas CMA at a space velocity equal to 1 V/V/H. However, ReS₂ /MgO is muchmore selective toward desulfurization as evidenced by the selectivityfactors. Consequently, under conditions necessary to desulfurize resid,i.e. T=400° C., P≧450 psig, SV=0.5-1 V/V/H, ReS₂ /MgO is as active (onmole % conversion basis) as CMA but is far more selective; thus thepreferred catalyst.

                                      TABLE VI                                    __________________________________________________________________________    cc             SV           Mole % x.sup.1                                                                         S.sup.2                                  Catalyst                                                                            (gm)                                                                              % M (V/V/H)                                                                            Hours on Stream                                                                        BP CHB                                                                              T  (Selectivity)                            __________________________________________________________________________    CMA   5   10  2    165      62.8                                                                             37.1                                                                             99.9                                                                             0.63                                           (3.91)  0.7  213      43.9                                                                             55.6                                                                             99.5                                                                             0.44                                     ReS.sub.2 /MgO                                                                      2.5 2.1 2-2.2                                                                              160      71 4.3                                                                              75.3                                                                             0.94                                           (1.74)  0.4-1                                                                              212      85 6  91 0.93                                     __________________________________________________________________________     ##STR12##                                                                     ##STR13##                                                                

What is claimed is:
 1. In a process for the hydrodesulfurization ofhydrocarbon feed streams wherein said hydrocarbon feedstreams arecontacted with a catalyst at a temperature and pressure and in thepresence of hydrogen or a hydrogen donor solvent and under conditionssufficient to effect the hydrodesulfurization of the hydrocarbonfeedstream, the improvement comprising using as the catalyst a layeredmaterial of the formula MX_(y) wherein M is a transition metal selectedfrom the groups consisting of Group IVb, Vb, VIb, VIIb metals, X is achalcogen selected from the group consisting of sulfur, selenium,tellurium and mixtures thereof and y is a number ranging from about 1.5to about 3 which material is prepared by reacting neat a Group IVb toVIIb metal salt, with a source of sulfide, selenide, or telluride ions,said source being selected from the group consisting of Li₂ X, Na₂ X, K₂X, NaHX, LiHX, KHX, (NH₄)HX, (NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X,(RR'R"NH)₂ X wherein R, R' and R" are the same or different C₁ -C.sub.20 alkyl group and C₆ -C₂₀ aryl group, and X is the chalcogen selectedfrom the group consisting of sulfur, selenium, tellurium and mixturesthereof, said reaction being conducted at a temperature of from -78 ° to400° C. for a time sufficient for reaction to occur.
 2. The process ofclaim 1 wherein the catalyst is ReS_(y) wherein y is from about 2 toabout
 4. 3. The process of claim 2 wherein the catalyst is ReS₂.
 4. Theprocess of claim 1 further characterized by the catalyst being depositedon high surface area supports selected from the group consisting of highsurface area carbon and high surface area refractory oxides.
 5. Theprocess of claim 1 wherein the chalcogen is sulfur.
 6. The process ofclaim 5 is about
 2. 7. The process of claim 1 wherein the transitionmetal is selected from Group VIb.
 8. The process of claim 4 wherein thehigh surface area support is selected from the group consisting of CaO,MgO, Al₂ O₃, silica-alumina and high surface area carbon.
 9. The processof claim 1 wherein the catalyst preparation temperature ranges from 25°to 300° C.
 10. In a process for the hydrodenitrogenation of hydrocarbonfeedstreams wherein said hydrocarbon feedstreams are contacted with acatalyst at a temperature and pressure and in the presence of hydrogenor a hydrogen donor solvent and under conditions sufficient to effectthe hydrodenitrogenation of the hydrocarbon feedstream, the improvementcomprising using as the catalyst a layered material of the formula MXywherein M is a transition metal selected from the group consisting ofGroup IVb, Vb, VIb, and VIIb transition metals, X is a chalcogenselected from the group consisting of sulfur, selenium, tellurium andmixtures thereof and y is a number ranging from about 1.5 to about 3which material is prepared by reacting neat a Group IVb to VIIb metalsalt with a source of sulfide, selenide or telluride ions, said sourcebeing selected from the group consisting of Li₂ X, Na₂ X, K₂ X, NaHX,LiHX, KHX, (NH₄)HX, (NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂ Xwherein R, R' and R" are the same or different C₁ -C₂₀ alkyl group andC₆ -C₂₀ aryl group and X is the chalcogen selected from the groupconsisting of sulfur, selenium, tellurium and mixtures thereof, saidreaction being conducted at a temperature of from -78° to 400° C. for atime sufficient for reaction to occur.
 11. The process of claim 10wherein the transition metal is selected from the group consisting ofGroup VIb transition metals.
 12. The process of claim 10 wherein thechalcogen is sulfur.
 13. The process of claim 11 wherein the chalcogenis sulfur.
 14. The process of claim 12 wherein y is
 2. 15. The processof claim 13 wherein y is about
 2. 16. The process of claim 10 whereinthe catalyst is ReS_(y) wherein y is from about 2 to
 3. 17. The processof claim 10 wherein the catalyst is ReS₂.
 18. The process of claim 10wherein the catalyst preparation temperature ranges from 25° to 300° C.19. The process of claim 17 wherein the catalyst preparation temperatureranges from 25° to 300° C.
 20. The process of claim 10 furthercharacterized by the catalyst being deposited on high surface areasupports selected from the group consisting of high surface area carbonand high surface area refractory oxides.
 21. The process of claim 20wherein the high surface area support is selected from the groupconsisting of CaO, MgO, Al₂ O₃, silica-alumina and high surface areacarbon.
 22. In a process for the hydrodesulfurization of hydrocarbonfeedstreams wherein said hydrocarbon feedstreams are contacted with acatalyst at a temperature and pressure and in the presence of hydrogenor a hydrogen donor solvent and under conditions sufficient to effectthe hydrodesulfurization of the hydrocarbon feedstream, the improvementcomprising using as the catalyst a layered material of the formulaMX_(y) wherein M is a transition metal selected from the groupconsisting of Group IVb, Vb, VIb, VIIb metals, X is a chalcogen selectedfrom the group consisting of sulfur, selenium, tellurium, and mixturesthereof and y is a number ranging from about 1.5 to about 3 whichmaterial is prepared by reacting in the presence of a nonaqueous,aprotic solvent a Group IVb to VIIb metal salt, with a source ofsulfide, selenide, or telluride ions, said source being selected fromthe group consisting of Li₂ X, Na₂ X, K₂ X, NaHX, LiHX, KHX, (NH₄)HX,(NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂ X, wherein R, R' and R" arethe same or different C₁ -C₂₀ alkyl group and C₆ -C₂₀ aryl group and Xis the chalcogen selected from the group consisting of sulfur, selenium,tellurium and mixtures thereof, said reaction being conducted at atemperature of from -78° to 400° C. for a time sufficient for reactionto occur.
 23. The process of claim 22 wherein the chalcogen is sulfur.24. The process of claim 23 wherein y is about
 2. 25. The process ofclaim 22 wherein the transition metal is selected from the groupconsisting of Group VIb transition metals.
 26. The process of claim 25wherein the chalcogen is sulfur.
 27. The process of claim 26 wherein yis about
 2. 28. The process of claim 22 wherein the catalyst is ReS_(y)wherein y is from about 2 to about
 4. 29. The process of claim 28wherein the catalyst is ReS₂.
 30. The process of claim 22 furthercharacterized by the catalyst being deposited on high surface areasupports selected from the group consisting of high surface area carbonand high surface area refractory oxides.
 31. The process of claim 29further characterized by the catalyst being deposited on high surfacearea supports selected from the group consisting of high surface areacarbon and high surface refractory oxides.
 32. The process of claim 30wherein the high surface area support is selected from the groupconsisting of CaO, MgO, Al₂ O₃, silica-alumina and high surface areacarbon.
 33. The process of claim 31 wherein the high surface areasupport is selected from the group consisting of CaO, MgO, Al₂ O₃,silica-alumina and high surface area carbon.
 34. The process of claim 22wherein the catalyst preparation temperature ranges from 25° to 300° C.35. The process of claim 29 wherein the catalyst preparation temperatureranges from 25° to 300° C.
 36. The process of claim 29 wherein thenonaqueous, aprotic solvent is selected from the group consisting ofacetonitrile, benzonitrile, propionitrile, acetone, C₁ -C₂₀ alkylhalides, C₆ -C₂₀ aryl halides, 1, 2-dimethoxyethane, diglyme,N-methylformamide, dimethylformamide, C₆ -C₂₀ aromatics, pyridine, C₁-C₁₂ alkanes, C₄ -C₈ ethers, anhydrous acids, propylene carbonate andthe hydrocarbon feedstream to be catalytically treated.
 37. The processof claim 29 wherein the catalyst is prepared in a catalytic reactorchamber by the addition of the appropriate starting material, thehydrocarbon feedstream to be catalytically treated being the nonaqueoussolvent.
 38. In a process for the hydrodenitrogenation of hydrocarbonfeedstreams wherein said hydrocarbon feedstreams are contacted with acatalyst at a temperature and pressure and in the presence of hydrogenor a hydrogen donor solvent and under conditions sufficient to effectthe hydrodenitrogenation of the hydrocarbon feedstream, the improvementcomprising using as the catalyst a layered material of the formulaMX_(y) wherein M is a transition metal selected from the groupconsisting of Group IVb, Vb, VIb, and VIIb metals, X is a chalcogenselected from the group consisting of sulfur, selenium, tellurium andmixtures thereof and y is a number ranging from about 1.5 to about 3which material is prepared by reacting in the presence of a nonaqueous,aprotic solvent a Group IVb to VIIb metal salt with a source of sulfide,selenide or telluride ions, said source being selected from the groupconsisting of Li₂ X, Na₂ X, K₂ X, NaHX, LiHX, KHX, (NH₄)HX, (NH₄)₂ X,(RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂ X wherein R, R' and R" are the sameor different C₁ -C₂₀ alkyl group and C₆ -C₂₀ aryl group, and X is thechalcogen selected from the group consisting of sulfur, selenium,tellurium and mixtures thereof, said reacting being conducted at atemperature of from -78 ° to 400° C. for a time sufficient for reactionto occur.
 39. The process of claim 38 wherein the transition metal isselected from the group consisting of Group VIb transition metals. 40.The process of claim 38 wherein the chalcogen is sulfur.
 41. The processof claim 39 wherein the chalcogen is sulfur.
 42. The process of claim 40wherein y is about
 2. 43. The process of claim 41 wherein y is about 2.44. The process of claim 38 wherein the catalyst is ReS_(y) wherein y isfrom about 2 to about
 3. 45. The process of claim 44 wherein thecatalyst is ReS₂.
 46. The process of claim 38 further characterized bythe catalyst being deposited on high surface area supports selected fromthe group consisting of high surface area carbon and high surface arearefractory oxides.
 47. The process of claim 45 further characterized bythe catalyst being deposited on high surface area supports selected fromthe group consisting of high surface area carbon and high surface arearefractory oxides.
 48. The process of claim 46 wherein the high surfacearea support is selected from the group consisting of CaO, MgO, Al₂ O₃,silica-alumina and high surface area carbon.
 49. The process of claim 47wherein the high surface area support is selected from the groupconsisting of CaO, MgO, Al₂ O₃, silica-alumina and high surface areacarbon.
 50. The process of claim 38 wherein the catalyst preparationtemperature ranges from 25° to 300° C.
 51. The process of claim 45wherein the catalyst preparation temperature ranges from 25° to 300° C.52. The process of claim 38 wherein the non-aqueous, aprotic solvent isselected from the group consisting of acetonitrile, benzonitrile,propionitrile, acetone, C₁ -C₂₀ alkyl halides, C₆ -C₂₀ aryl halides,1,2-dimethoxyethane, diglyme, N-methylformamide, dimethylformamide, C₆-C₂₀ aromatics, pyridine, C₁ -C₁₂ alkanes, C₄ -C₈ ethers, anhydrousacids, propylene carbonate, ammonia, molten sulfur, C₁ -C₃₀ amine andthe hydrocarbon feedstream to be catalytically treated.
 53. The processof claim 45 wherein the nonaqueous, aprotic solvent is selected from thegroup consisting of acetonitrile, benzonitrile, propionitrile, acetone,C₁ -C₂₀ alkyl halides, C₆ -C₂₀ aryl halides, 1,2-dimethoxyethane,diglyme, N-methylformamide, dimethylformamide, C₆ -C₂₀ aromatics,pyridine, C₁ -C₁₂ alkanes, C₄ -C₈ ethers, anhydrous acids, propylenecarbonate, ammonia, molten sulfur, C₁ -C₃₀ amines and the hydrocarbonfeedstock to be catalytically treated.
 54. The process of claim 38wherein the catalyst is prepared in a catalytic reactor chamber by theaddition of the appropriate starting material, the hydrocarbonfeedstream to be catalytically treated being the nonaqueous solvent. 55.The process of claim 45 wherein the catalyst is prepared in a catalyticreaction chamber by the addition of the appropriate starting material,the hydrocarbon feedstream to be catalytically treated being thenonaqueous solvent.
 56. In a process for the hydrogenation in thepresence of hydrogen or a hydrogen donor solvent of hydrocarbonfeedstreams wherein said hydrocarbon feedstreams are contacted with acatalyst at a temperature and pressure and under conditions sufficientto effect the hydrogenation of the hydrocarbon feedstream, theimprovement comprising using as a catalyst a layered material of theformula MX_(y) wherein M is a transition metal selected from the groupconsisting of Group IVb,Vb, VIb,VIIb metals, X is a chalcogen selectedfrom the group consisting of sulfur, selenium, tellurium and mixturesthereof and y is a number ranging from about 1.5 to about 3 whichmaterial is prepared by reacting in the presence of a nonaqueous,aprotic solvent a Group IVb to VIIb metal salt, with a source ofsulfide, selenide, or telluride ions, said source being selected fromthe group consisting of Li₂ X, Na₂ X, K₂ X, NaHX, LiHX, KHX, (NH₄)HX,(NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂ X wherein R, R' and R" arethe same or different C.sub. 1 -C₂₀ alkyl group and C₆ -C₂₀ aryl group,and X is the chalcogen selected from the group consisting of sulfur,selenium, tellurium and mixtures thereof, said reaction being conductedat a temperature of from -78° to 400° C. for a time sufficient forreaction to occur.
 57. The process of claim 56 wherein the transitionmetal is selected from the group consisting of Group VIb and Group VIIbtransition metals.
 58. The process of claim 56 wherein the chalcogen issulfur.
 59. The process of claim 57 wherein the chalcogen is sulfur. 60.The process of claim 58 wherein y is about
 2. 61. The process of claim59 wherein y is about
 2. 62. The process of claim 56 wherein thecatalyst is ReS_(y) wherein y is from about 2 to about
 3. 63. Theprocess of claim 62 wherein the catalyst is ReS₂.
 64. The process ofclaim 56 further characterized by the catalyst being deposited on highsurface area supports selected from the group consisting of high surfacearea carbon and high surface area refractory oxides.
 65. The process ofclaim 63 further characterized by the catalyst being deposited on highsurface area supports selected from the group consisting of high surfacearea carbon and high surface area refractory oxides.
 66. The process ofclaim 64 wherein the high surface area support is selected from thegroup consisting of CaO, MgO, Al₂ O₃, silica-alumina and high surfacearea carbon.
 67. The process of claim 65 wherein the high surface areasupport is selected from the group consisting of CaO, MgO, Al₂ O₃,silica-alumina and high surface area carbon.
 68. The process of claim 56wherein the catalyst preparation temperature ranges from 25° to 300° C.69. The process of claim 63 wherein the catalyst preparation temperatureranges from 25° to 300° C.
 70. The process of claim 56 wherein thenonaqueous aprotic solvent is selected from the group consisting ofacetonitrile, benzonitrile, propionitrile, acetone, C₁ -C₂₀ alkylhalides, C₆ -C₂₀ aryl halides, 1,2-dimethoxyethane, diglyme,N-methylformamide, dimethylformamide, C₆ -C₂₀ aromatics, pyridine, C₄-C₈ ethers, anhydrous acids, propylene carbonate, ammonia, moltensulfur, C₁ -C₃₀ amines, C₁ -C₁₂ alkanes, and the hydrocarbon feedstreamto be catalytically treated.
 71. The process of claim 63 wherein thenonaqueous aprotic solvent is selected from the group consisting ofacetonitrile, benzonitrile, propionitrile, acetone, C₇ -C₂₀ alkylhalides, 1,2-dimethoxyethane, diglyme, N-methylformamide,dimethylformamide, C₆ -C₂₀ aromatics, pyridine, C₄ -C₈ ethers, anhydrousacids, propylene carbonate, ammonia, molten sulfur, C₁ -C₃₀ amines, C₁-C₁₂ alkanes and the hydrocarbon feedstream to be catalytically treated.72. The process of claim 56 wherein the catalyst is prepared in acatalytic reactor chamber by the addition of the appropriate startingmaterial, the hydrocarbon feedstream to be catalytically treated beingthe nonaqueous solvent.
 73. The process of claim 63 wherein the catalystis prepared in a catalytic reactor chamber by the addition of theappropriate starting material, the hydrocarbon feedstream to becatalytically treated being the nonaqueous solvent.
 74. The process ofclaim 22 wherein the non-aqueous, aprotic solvent is selected from thegroup consisting of acetonitrile, benzonitrile, propionitrile, acetone,C₁ -C₂₀ alkyl halides, C₆ -C₂₀ aryl halides, 1,2-dimethoxyethane,diglyma, N-methylformamide, dimethylformamide, C₆ -C₂₀ aromatics,pyridine, C₁ -C₁₂ alkanes, C₄ -C₈ ethers, anhydrous acids, propylenecarbonate and the hydrocarbon feed stream to be catalytically treated.75. The process of claim 22 wherein the catalyst is prepared in acatalytic reactor chamber by the addition of the appropriate startingmaterial, the hydrocarbon feed stream to be catalytically treated beingthe non-aqueous solvent.
 76. The process of claim 17 furthercharacterized by the catalyst being deposited on high surface areasupports selected from the group consisting of high surface area carbonand high surface area refractory oxides.
 77. The process of claim 76wherein the high surface area support is selected from the groupconsisting of CaO, MgO, Al₂ O₃, silica-alumina and high surface areacarbon.
 78. In a process for the hydrogenation of hydrocarbonfeedstreams wherein said hydrocarbon feedstreams are contacted with acatalyst at a temperature and pressure and in the presence of hydrogenor a hydrogen donor solvent and under conditions sufficient to effectthe hydrogenation of the hydrocarbon feedstreams, the improvementcomprising using as the catalyst a layered material of the formulaMX_(y) wherein M is a transition metal selected from the groupconsisting of Group IVb, Vb, VIb, VIIb metals X is a chalcogen selectedfrom the group consisting of sulfur, selenium, tellurium and mixturesthereof and y is a number ranging from about 1.5 to about 3 whichmaterial is prepared by reacting neat a Group IVb to VIIb metal salt,with a source of sulfide, selenide, or telluride ions, said source beingselected from the group consisting of Li₂ X, Na₂ X, K₂ X, NaHX, LiHX,KHX, (NH₄)HX, (NH₄)₂ X, (RNH₃)₂ X, (RR'NH₂)₂ X, (RR'R"NH)₂ X wherein R,R' and R" are the same or different C₁ -C₂₀ alkyl group and C₆ -C₂₀ arylgroup and X is the chalcogen selected from the group consisting ofsulfur, selenium, tellurium and mixtures thereof, said reaction beingconducted at a temperature of from -78 to 400° C. for a time sufficientfor reaction to occur.
 79. The process of claim 78 wherein thetransition metal is selected from the group consisting of Group VIbtransition metals.
 80. The process of claim 78 wherein the chalcogen issulfur.
 81. The process of claim 80 wherein y is about
 2. 82. Theprocess of claim 79 wherein the chalcogen is sulfur.
 83. The process ofclaim 82 wherein y is about
 2. 84. The process of claim 78 wherein thecatalyst is ReS_(y) wherein y is from about 2 to about
 3. 85. Theprocess of claim 84 wherein the catalyst is ReS₂.